JPH0860052A - Ink composition and color filter produced using the same - Google Patents

Abstract

PURPOSE: To obtain an ink compsn. which is excellent in physical and chemical stability and useful for obtaining an inexpensive color filter excellent in optical characteristics by incorporating a specific compd. into the compsn. CONSTITUTION: The compsn. contains at least one compd. represented by the formula [wherein Pc is an optionally metal-contg. phthalocyanine residue; A is OM, NHCH2 COOM, NHC2 H4 SO3 M, etc.; B is ON, NH2 , etc.; M is H, Na, K, Li, NH4 , NH3 CH2 CH2 OH, NH2 (CH2 CH2 OH)2 , or NH(CH2 CH2 OH)3 ; α is 1-3; β is 0-2; γ is 1-4 provided α+β+γ is 4 or lower; and SO3 M, SO2 B, and SO2 B are bonded to different benzene rings of the phthalocyanine residue].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter ink composition and an ink jet system for use in the production of color filters having excellent optical properties used in liquid crystal display devices, color separation devices, sensors and the like. Relates to the color filter manufactured in.

[0002]

2. Description of the Related Art Conventionally, a method of combining three primary color filters of red, green, blue, or yellow, magenta, and cyan has been used for colorizing a liquid crystal display device or a solid-state image pickup device. Although there are several methods for forming these color filters, the most basic method is the so-called dyeing method. The color filter is produced by a dyeing method, which is a film of a synthetic resin having a thin film-like transparent cationic group such as a stripe or mosaic (referred to as a pattern) on the surface of a substrate such as glass or silicon wafer. Alternatively, the basic principle is to provide a film of a protein-based natural polymer such as gelatin, casein, or glue to form a film to be colored, and dye (color) this with a dye. The following three methods are known as specific manufacturing processes of the color filter.

(1) After a film to be colored is provided on the surface of the substrate, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer. Then a non-coloring protective coat
A coating film is provided on the entire surface, and a second coating film to be colored is provided thereon by the same operation as above. Hereinafter, if necessary, colored layers are sequentially laminated.

(2) After a film to be colored is provided on the surface of the substrate, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer, and then a dye is fixed with tannic acid or the like. Combined with dye-proof treatment. A second coating to be colored is provided by the same operation. Thereafter, if necessary, a colored layer is formed on the same substrate surface.

(3) A film to be colored (coloring film) is provided on the surface of the substrate. After providing a positive resist layer thereon, the film to be colored is exposed and developed through a mask to dye the exposed film to be colored, and then the positive resist layer is peeled off to form a colored portion. By repeating the operation after providing the positive resist layer, the same colored film is dyed into a desired pattern in a plurality of colors.

Color produced by the above process
Except for special ones, the filters are usually the three primary colors R (red), G (green), B (blue) or the complementary three primary colors Y (yellow), M (magenta), C (cyan). ), (M may be omitted). The most important characteristic required for the color filter is the optical characteristic, and the spectral characteristic of each colored layer greatly controls the value of the final product.

In addition, for heat treatment encountered in the process of manufacturing a liquid crystal display device having a color filter, for example, for a sputtering process for providing a transparent electrode layer, and for light applied during use as a final product. It must have a high degree of resistance and must not impair certain optical properties. Of course, the dyes applied must also have good solubility and solubility in water and be stable for a long time in acidic dye baths.

Further, in the case of involving a step requiring fixing treatment, it is required that the fixing treatment effect is excellent. By the way, since protein-based polymer substances such as gelatin, casein, and glue have a cationic group, they are dyed (colored) with a water-soluble anionic dye. When a photo-curable synthetic resin substrate is used instead of these, by retaining a cationic group in the resin component, it is dyed with a water-soluble anionic dye like a protein-based natural polymer substance. Become so.

As described above, the dyeing method has a feature that an extremely fine color pattern can be freely formed.
Since many manufacturing processes such as a photolithography process, a dyeing process, and a cleaning / fixing process are performed depending on the number of colors to be dyed, there is a high risk that yield may be reduced due to dust adhesion during manufacturing. Further, since the coloring density is almost proportional to the film thickness of the dyed resin film, the fluctuation of the film thickness causes unevenness of color and deteriorates the quality of the product. Depending on the order of dyeing, color unevenness may occur due to contamination or desorption of other colors. Further, a liquid crystal display device manufacturer has strongly demanded a method of reducing the number of steps for manufacturing a color filter to improve the yield and make the cost lower.

[0010]

SUMMARY OF THE INVENTION According to the present invention, a highly dyeable photosensitive resin thin film is formed on a substrate, and a dye solution is selectively jetted onto the thin film layer by an inkjet method to form a desired colored pattern. Then, it is to provide an ink composition suitable for obtaining a color filter by fixing treatment and a color filter manufactured using the same.

[0011]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems, and as a result, achieved the present invention. That is, the present invention provides (1) general formula (1)

[0012]

[Chemical 10]

(In the formula (1), Pc is a metal-free or metal-containing phthalocyanine residue, A is --OM, --NHCH ₂ C
OOM, —NHC ₂ H ₄ SO ₃ M, or

[0014]

[Chemical 11]

B is --OM, --NH ₂ or

[0016]

[Chemical 12]

(Wherein R ₁ and R ₂ are H, --CH ₃ , --C
OOM, -NHCOCH _3, -NHCONH _2, a halogen or an alkoxy group having 1 to 3 carbon atoms, C is

[0018]

[Chemical 13]

(Where Y is H,

[0020]

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(In the formula, R ₃ , R ₄ are H, -OM, -CO
_{OM, CH 3 SO 2 -,} CH 3 CONH -, - NH 2,
An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or halogen, and m represents an integer of 0, 1 or 2) or

[0022]

[Chemical 15]

(In the formula, p represents an integer of 0, 1, 2 or 3), and Z is —CH ₃ , —C ₂ H ₅ , —COOM or —.
NH ₂ respectively);

[0024]

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(In the formula, R ₅ is —CONH ₂ , —CH ₂ S
O ₃ M or —CN, R ₆ is an alkyl group having 1 to 4 carbon atoms, — (CH ₂ ) _q —COOM (q represents 1, 2 or 3), — (CH ₂ ) _q —SO ₃ M (q represents the same meaning as described above) or a hydroxyalkyl group having 1 to 3 carbon atoms, respectively;

[0026]

[Chemical 17]

(M has the same meaning as above) or

[0028]

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(P represents the same meaning as described above), and n is 0
Or 1 respectively. Further, α represents a number of 1 to 3, β represents a number of 0 to 2, and γ represents a number of 1 to 4, respectively, and α + β + γ is 4 or less. Also, SO ₃ M, SO ₂ bound to Pc
Each of A and SO ₂ B is bound to a non-identical benzene ring of a phthalocyanine residue, the metal when Pc contains a metal is copper, zinc, aluminum or nickel, M is H, Na, K, Li, NH ₄ , NH
_{3 represents} CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ or NH (CH ₂ CH ₂ OH) ₃ . ) Ink composition comprising at least one compound represented by the formula (2), (2) Ink composition for producing a color filter comprising at least one compound according to (1) above. (3) An ink composition for producing a color filter by an inkjet method, which comprises at least one of the compounds described in (1) above, (4) The ink composition described in (1) above. The present invention relates to a color filter manufactured by coloring by using an inkjet method.

Specific examples of the compound of the general formula (1) used in the present invention include the following.

[0031]

[Chemical 19]

[0032]

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[0033]

[Chemical 21]

[0034]

[Chemical formula 22]

[0035]

[Chemical formula 23]

[0036]

[Chemical formula 24]

[0037]

[Chemical 25]

[0038]

[Chemical formula 26]

[0039]

[Chemical 27]

[0040]

[Chemical 28]

[0041]

[Chemical 29]

[0042]

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[0043]

[Chemical 31]

[0044]

[Chemical 32]

[0045]

[Chemical 33]

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

[Chemical 38]

[0051]

[Chemical Formula 39]

[0052]

[Chemical 40]

[0053]

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[0054]

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The liquid medium of the ink composition of the present invention includes
A liquid medium containing at least water or preferably ion-exchanged water and a hydrophilic organic solvent is used. Here, the hydrophilic organic solvent has an effect as a non-drying agent, has a role of preventing the generation of solid matter by drying, and also has a role of adjusting the viscosity of the ink composition. The liquid medium must be selected so as not to interfere with the dissolution of the compound represented by the general formula (1). As a hydrophilic organic solvent,
For example, alcohols such as methyl alcohol, ethyl alcohol and butyl alcohol, polyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol, polyalkylene glycol alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, ethylene Glycol,
Alkylene glycols such as propylene glycol and butylene glycol, cellusolves such as methylcellosolve and ethylcellosolve, nitrogen-containing heterocycles such as glycerin, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone One or more of the formula ketones, dimethylformamide, dimethylacetamide and the like can be used as a liquid medium component by mixing them if necessary. The content of the hydrophilic organic solvent in the ink composition is generally 0 to 50% by weight, preferably 3 to 40% by weight, more preferably 5 to 25% by weight, based on the total weight of the ink liquid. It is better to let them do it.

In the ink composition of the present invention, a solubilizing agent can be added so that the dye does not precipitate in the composition. Examples of the solubilizing agent include urea and ε-caprolactam. If necessary, these solubilizing agents may be contained in the composition in an amount of 1 to 30% by weight, preferably 1 to 20%.

The dye used in the present invention has the structure of the above formula (1). Generally, inorganic salts such as sodium chloride and sodium sulfate are mixed in during the synthesis of these dyes.
Further, calcium ions, magnesium ions, etc. contained in general water are mixed in in a trace amount. These inorganic components not only significantly deteriorate the solubility and storage stability of the dye, but also cause corrosion and wear of the printer head. Methods such as ultrafiltration, reverse osmosis, and ion exchange are used to remove these inorganic salts, and it is desirable to remove inorganic salts as much as possible, but in practice, standards are set and managed. There must be. The content is required to be at least 1% by weight or less with respect to the compound of the formula (1), preferably 0.5% by weight or less, more preferably 0.1% by weight or less.

Although the desired dye concentration is obtained by diluting or concentrating after removing the inorganic salts, the ink composition of the present invention can contain a dye content of 1 to 10% by weight, and practically 3 to 5 is used. Weight percent is preferred. After being prepared from such components, liquid filtration is performed using a cellulosic filter aid to remove dust, foreign substances, and other impurities, and then microfiltration is performed using a membrane filter (pore size 1 micron). It is preferable to perform microfiltration with a membrane filter having a pore size of 0.45 micron.

Among the various characteristics, the ink composition of the present invention prepared by mixing and preparing as described above is particularly excellent in stability and long-term storability, and is characterized in that the ejection orifice is not clogged. In addition, a stabilizer for the ink composition (for example, sodium polyacrylate such as Kayakerator C manufactured by Nippon Kayaku Co., Ltd.)
-1000 etc.) and antibacterial / antifungal agents (for example, Deltop manufactured by Takeda Pharmaceutical Co., Ltd.), it is advisable to add them before the microfiltration.

The color filter of the present invention can be manufactured, for example, as follows. That is, a coating film is formed by a spin coating method or the like using a protein-based natural polymer substance by the method described below, or a highly dyeable photosensitive resin is dissolved in a solvent such as methylcellosolve acetate, and the spin coating method or the like is used. The substrate is coated with the photosensitive resin liquid by a method, and the substrate is dried and then exposed to light to cure the photosensitive resin. The film thickness of the photosensitive resin thin film is preferably 0.2 to 5 μm, particularly 0.5 to 1.5 μm.
m is preferred. The photosensitive resin thin film may be exposed to a predetermined pattern through a mask, or may be exposed to the front surface without a pattern and cured. When a pattern is provided, a partition may be formed as a black matrix in the gap between the patterns. At a predetermined place of the photosensitive resin thin film thus obtained, by a method such as an inkjet method or a bubble jet method,
A predetermined amount of the ink composition of the present invention is attached. Coloring by the inkjet method may be performed for each color or for multiple colors simultaneously. After coloring, heat drying treatment is performed for 3 to 15 minutes on a hot plate or oven at 70 to 180 ° C. After that, in order to prevent the dye from being eluted, a fixing treatment is carried out in an aqueous solution of tannic acid and tartarite to wash. Further, for the purpose of protecting the color filter layer, a transparent protective layer may be coated on the entire surface of the colored thin film.

The substrate used in the present invention is not particularly limited as long as it is a colorless and transparent plate, and examples thereof include plates made of glass, polyester, polycarbonate, polyacrylate, polyether sulfone and the like. Its thickness is 0.5
About 1.5 mm is preferable.

The protein type natural polymer substances such as gelatin, casein, glue and the like as the film to be colored in the present invention will be explained. Gelatin is an animal protein in which collagen is boiled with water to irreversibly convert it to water-soluble. It is extracted from animal bones, skin, tendons and the like by boiling with water.
Casein is a phosphoprotein that is the main component of milk. A dichromate such as ammonium dichromate is added to an aqueous solution of these natural proteins, and the spin coat method and roller coat method are used.
When the composition is uniformly coated on a substrate such as glass by a coating method or the like and then irradiated with ultraviolet rays, the coating layer is cured and a water-insoluble film is formed.

Further, as an example of the synthetic resin having a cationic group as the material to be colored used in the present invention, a polymer having an unsaturated group capable of photoreacting in the side chain and a quaternary ammonium salt group is photopolymerized. A resin composition comprising an initiator and a solvent, or a photo-crosslinking group such as a chalcone group, a cinnamic acid group, an azide group, a stilbazol group or an epoxy group is previously polymerized.
A resin composition in which a cationic group-containing polymer introduced therein is dissolved in water or an organic solvent, or a nitrogen-containing monomer
As one of the essential constituents, a polymer obtained by polymerization is added with a photocrosslinking agent such as a diazo compound, an azide or a diazide compound, and a resin composition diluted with an organic solvent. Such a photoreactive resin composition is applied to the surface of a substrate and cured by irradiation with actinic rays such as ultraviolet rays to obtain a film. Specific examples of the resin composition suitable for obtaining the color filter of the present invention include, for example, CFR633L1 (manufactured by Nippon Kayaku Co., Ltd.), CFR-3 (manufactured by Nippon Kayaku Co., Ltd.), CF.
R-5 (Nippon Kayaku Co., Ltd.), R-102 (Nippon Kayaku Co., Ltd.), JDS-509 (Nippon Synthetic Rubber Co., Ltd.)
Etc. are preferred.

The water-soluble phthalocyanine compound represented by the general formula (1) is produced, for example, by the following method.
That is, equation (2)

[0065]

[Chemical 43]

(In the formula (2), Pc, M, α, β and γ have the same meanings as described above) and a sulfonic acid chloride compound represented by the formula (3) H—A (3) (wherein A represents the same meaning as described above) or a compound of formula (2) and a compound of formula (3) and formula (4)

[0067]

[Chemical 44]

It can be obtained by condensing a compound represented by the formula (4), wherein C, M, R ₁ , R ₂ and n have the same meanings as described above. A condensation reaction between the compound represented by formula (2) and the compound represented by formula (3), or the formula (2)
The condensation reaction between the compound represented by formula (3) and the compound represented by formula (3) or formula (4) is carried out in water, in an aqueous organic solvent or in an organic solvent at a temperature of 0 to 100 ° C. and a PH value of 2 to 12 with an acid binder. In the presence of. As the acid binder in these condensation reactions, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are used. A usual separation method such as an acid precipitation method or a salting out method is applied to the separation of the desired product from the reaction solution thus obtained.

Specific examples of the compound represented by the formula (3) include the followings. (In the examples, the sulfonic acid group and the carboxyl group are represented in the form of free acid.
The same applies below. )

[0070]

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Specific examples of the compound represented by the formula (4) include the following.

[0072]

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[0073]

[Chemical 47]

[0074]

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[0075]

[Chemical 49]

[0076]

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[0077]

[Chemical 51]

[0078]

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[0079]

Embedded image

[0080]

[Chemical 54]

[0081]

[Chemical 55]

[0082]

[Chemical 56]

In the formula (1), the compound in which B is NH ₂ is the sulfonic acid chloride compound of the formula (2) and the compound of the formula (3).
And a compound that releases ammonia, such as ammonium chloride or ammonium chloride or ammonium acetate. Further, for the compound of formula (1) in which B is OH, the sulfonic acid chloride compound of formula (2) and the compound of formula (3) are condensed and then subjected to heat treatment in an aqueous medium to hydrolyze the sulfonyl chloride group. Can be obtained by

Next, the present invention will be described in more detail with reference to synthetic examples and examples, but the present invention is not limited to these examples. In the text, parts and% are based on weight. Synthesis example 1. No. Synthesis of compound 1

[0085]

[Chemical 57]

100 parts of an aqueous solution containing 9.46 parts of the amino compound represented by the formula and adjusted to pH 7.5 was stirred at 10 ° C.
Copper phthalocyanine-tetrasulfonic acid chloride 1 below
9.4 parts are added as a wet paste. Then, 50 parts of an aqueous solution in which 2.78 parts of P-nitrophenol is completely dissolved in an alkaline solution is added. Then, by adding 10% liquid caustic aqueous solution at 10 to 20 ° C., the PH value was adjusted to 9.0 to 10.0
The reaction was carried out for 12 hours while maintaining Then, the temperature was raised to 70 ° C. and the reaction was carried out at this temperature for 2 hours. Thereafter, the pH value was adjusted to 6.0 with dilute hydrochloric acid, and the obtained crystals were salted out with sodium chloride, filtered off, dried at 60 ° C. and dried. 26.0 parts of compound 1 were obtained. The wavelength showing the maximum transmittance of the obtained compound in water (λ _{Tmax and} below) is 526 n.
m, and the maximum absorption wavelengths were 425 nm and 667 nm.

Synthesis Example 2. No. Synthesis of Compound 2 Synthesis Example 1. Under stirring to 100 parts of an aqueous solution adjusted to pH 7.5 containing 9.46 parts of the amino compound used in 1.
At 0 ° C. or lower, 19.4 parts of copper phthalocyanine-tetrasulfonic acid chloride is added as a wet paste. Then 1
The reaction was carried out for 12 hours while maintaining the PH value at 9.0 to 10.0 by adding a 10% caustic aqueous solution at 0 to 20 ° C.
Then, the temperature was raised to 70 ° C. and the reaction was carried out at this temperature for 2 hours.
Thereafter, the pH value was adjusted to 6.0 with dilute hydrochloric acid, and the obtained crystals were salted out with sodium chloride, filtered off, dried at 60 ° C. and dried. 24.0 parts of compound 2 were obtained. The wavelength (λ _Tmax ) showing the maximum transmittance in water of the obtained compound is 525 nm, and the maximum absorption wavelength is 425 nm, 667.
was nm.

Synthesis Example 3. No. Synthesis of the compound of 3. Into 200 parts of an aqueous solution in which 3.68 parts of 2,4-dinitrophenol were completely dissolved in PH10, with stirring, 10.4 parts of zinc phthalocyanine-trisulfonic acid chloride was wet paste at 10 ° C or lower. Added as. Then 10 ~ 15 ℃
Then, by adding 10% caustic aqueous solution, the PH value becomes 10.0-
The reaction was carried out for 15 hours while maintaining it at 11.0. Then 5
The temperature was raised to 0 ° C., and the reaction was carried out at this temperature for 3 hours. Then, the pH value was adjusted to 3 with dilute hydrochloric acid and salted out with sodium chloride, the obtained crystals were filtered off, dried at 80 ° C. 19.5 parts of the dye compound of 3 were obtained. (Λ _Tmax 49
8 nm)

Example 1 No. The pH of the reaction solution containing 8 parts of the compound of 1 is adjusted to 6 to 8 and then filtered to remove insoluble matter. Next, desalting was carried out by the reverse osmosis method to obtain inorganic salts, 0.5% for 1 compound
The following is added to this solution.

Ε-Caprolactam 10 parts Propylene glycol 5 parts Kayachelator C-1000 1 part Deltop 0.3 parts

After this liquid was filtered again, it was further microfiltered with a membrane filter having a pore size of 1 micron and a membrane filter having a pore size of 0.45 micron, and ion-exchanged water (filtered with a membrane filter having a pore size of 0.45 micron: The same applies hereinafter) so that the total amount becomes 100 parts to obtain an ink composition for a color filter of the inkjet printing method of the present invention. This color filter ink composition exhibited good stability for one month or longer at room temperature and low temperature (-5 ° C).

Example 2 No. The pH of the reaction solution containing 5 parts of the compound of 2 is adjusted to 6 to 8 and then filtered to remove insoluble matter. Next, it was desalted by the reverse osmosis method to remove inorganic salts from 0.5% or less based on the compound of 2, and the following substances are added to this liquid.

Urea 5 parts Ethyl cellosolve 5 parts Kayachelator C-1000 1 part Deltop 0.3 parts

After liquid filtration of this liquid again, microfiltration was further performed with a membrane filter having a pore size of 1 micron and a membrane filter having a pore size of 0.45 micron, and the total amount was adjusted to 100 parts with ion-exchanged water. To obtain an ink composition for a color filter of the inkjet printing method. This color filter ink composition exhibited good stability for one month or longer at room temperature and low temperature (-5 ° C).

Example 3 Dyeable photosensitive resin liquid CFR-3 (manufactured by Nippon Kayaku Co., Ltd.) 1
00 parts and 0.05 part of silane coupling agent KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. This is coated on a glass plate by a spin coating method, dried at 110 ° C. for 3 minutes, and then exposed through a belt conveyor type UV irradiator and cured. The exposure amount was about 150 mJ / cm ² . The glass substrate having the thin film to be dyed thus formed is accurately positioned by an optical prescription and set in an inkjet printer. The green ink composition described in Example 1 (4% aqueous solution of the compound of No. 1) was added to 0.2%.
The solution is passed through a 2 μm membrane filter and jetted as an dyeing solution with an ink jet to adhere to the portion to be colored green of the thin film to be dyed. This is dried by heating on a hot plate heated to 150 ° C. for 10 minutes. Next, as dye fixation treatment, 3 g of tannin, 1 g of tartar in 1 liter of water,
The dyed glass substrate is immersed in a solution containing 3 g of acetic acid, treated at 70 ° C. for 7 minutes, washed with water, and dried at 130 ° C. for 10 minutes.
After drying for a minute, a color filter having a green pattern was obtained. This green color filter has a substantially square pattern of about 150 μm, and has the same performance as a color filter formed by a conventional so-called dyeing method.

Example 4 Dyeable photosensitive resin liquid CFR-3 (manufactured by Nippon Kayaku Co., Ltd.) 1
00 parts and 0.05 part of silane coupling agent KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. This is coated on a glass plate by a spin coating method, dried at 110 ° C. for 3 minutes, and then exposed through a belt conveyor type UV irradiator and cured. The exposure amount was about 150 mJ / cm ² . The glass substrate having the thin film to be dyed thus formed is accurately positioned by an optical prescription and set in an inkjet printer. The green ink composition described in Example 2 (4% aqueous solution of the compound of No. 2) was added to 0.2%.
The solution is passed through a 2 μm membrane filter and jetted as an dyeing solution with an ink jet to adhere to the portion to be colored green of the thin film to be dyed. This is dried by heating on a hot plate heated to 150 ° C. for 10 minutes. Next, as a dye fixing treatment, the dyed glass substrate is immersed in a solution containing 3 g of tannin, 1 g of tartar, and 3 g of acetic acid in 1 liter of water,
After treating at 70 ° C. for 7 minutes, it was washed with water and dried at 130 ° C. for 10 minutes to obtain a color filter having a blue pattern. This green color filter has a substantially square pattern of about 150 μm, and has the same performance as a color filter formed by a conventional so-called dyeing method.

Example 5 A glass substrate having a black stripe formed by a conventional method was spin-coated with a spinner a photosensitive resin composed of a mixture of a water-soluble nylon resin and a stilbazolium-based resin in a thickness of 1 μm, at 90 ° C. After drying for 15 minutes, the entire surface of the glass was exposed. Then, it was immersed in water for 2 minutes and developed to obtain a dyeable resin film having a black stripe on the substrate. This glass substrate was set in an inkjet printer in the same manner as in Example 3, and the ink composition described in Example 1 was used to eject the glass substrate to form a color filter.

Examples 6 to 49 Compounds were synthesized by the above-described synthesis method, aqueous ink compositions were prepared according to Examples 1 to 5, and a color filter was manufactured by an inkjet method using the same. Table 1
5, compound No. used and its content by weight, additive composition (type of organic solvent and / or solubilizer and its content by weight), hue of colored film, transmission maximum wavelength λ of colored film
_{The Tmax} (nm) was shown. In the table, EG is ethylene glycol, DG is diethylene glycol, TG is triethylene glycol, PEG is polyethylene glycol, and PG.
Is propylene glycol, ME is methylcellosolve, E
E means ethyl cellosolve, NMP means N-methylpyrrolidone, and CR means ε-caprolactam.

[0099]

[Table 1] Table 1 Examples Compound No. (wt%) Additive composition (wt%) Colored film Color of maximum transmission Wavelength (nm) 6 6 (5) EE 10 Yellowish green 530 7 7 (4) EG 5 Yellow Taste green 537 8 8 (4) Urea 2 Yellowish green 534 9 9 (6) PEG 5 Yellowish green 530 10 10 (6) DG 5 Yellowish green 530 11 11 (8) DG 5 Yellowish green 537 NMP 5 12 12 (5) PG 3 Yellowish green 534 13 13 (4) Urea 5 Yellowish green 530 TG 10 14 14 (2) ME 10 Yellowish green 538

[0100]

[Table 2] Table 2 Examples Compound No (wt%) Additive composition (wt%) Colored film Hue of transmission maximum Wavelength (nm) 15 15 (2) Urea 5 Blue-green 500 PEG 10 16 16 (4) EE 20 green 518 17 17 (4) EE 30 yellowish green 530 18 18 (5) urea 5 bluish green 503 PG 10 19 19 (5) urea 5 bluish green 504 PG 15 20 20 (4) CR 2 bluish green 502 EE 10 21 21 (4) CR 5 bluish green 503 EE 15 22 22 (4) EG 10 bluish green 502 23 23 (4) EG 15 bluish green 505

[0101]

[Table 3] Table 3 Examples Compound No. (wt%) Additive composition (wt%) Colored film Transmission maximum hue Wavelength (nm) 24 24 (5) Urea 2 Blue green 508 PG 15 25 25 (5) Urea 2 Green 515 PG 20 26 26 (3) EE 20 Blue Green 508 27 27 (4) EE 25 Blue Green 509 28 28 (5) NMP 2 Green 511 EE 25 29 29 (4) NMP 2 Blue Green 507 EE 20 30 30 (6) Urea 5 bluish green 503 EE 30 31 31 (5) Urea 5 green 518 EE 20 32 32 (4) CR 5 bluish green 536 PEG 25

[0102]

[Table 4] Table 4 Examples Compound No. (wt%) Additive composition (wt%) Colored film Hue of transmission maximum Wavelength (nm) 33 33 (5) CR 5 Reddish green 546 PEG 20 34 34 (5) NMP 5 Red Green 544 EE 20 35 35 (4) PEG Red Green 540 36 36 (5) EE 40 Blue 493 37 37 (4) Urea 5 Blue 493 38 38 (5) Urea 5 Blue 496 PG 5 39 39 (4) ) Urea 5 Blue 492 40 40 (4) DG 20 Blue 497 41 41 (4) TG 20 Blue 496

[0103]

[Table 5] Table 5 Examples Compound No. (wt%) Additive composition (wt%) Colored film Transmission maximum hue Wavelength (nm) 42 42 (5) Urea 5 Blue 494 DG 30 43 43 (5) Urea 5 Blue 493 TG 20 44 44 (3) CR 5 Blue 492 EE 20 45 45 (5) EE 15 Blue 493 46 46 (4) CR 5 Blue 493 PEG 15 47 47 (4) Urea 2 Blue 494 PEG 18 48 48 (5) PG 25 Blue 495 49 49 (4) NMP 5 Blue 499 PG 20

[0104]

EFFECT OF THE INVENTION By using an ink composition containing a metal-free or metal-containing specific phthalocyanine compound to produce a color filter by an inkjet method, an inexpensive and high-quality color filter can be obtained. . Moreover, this ink composition is advantageous because it has high chemical and physical stability.

Claims (4)

[Claims] 1. A general formula (1): (In the formula (1), Pc is a metal-free or metal-containing phthalocyanine residue, and A is —OM, —NHCH ₂ COOM, —N.
HC ₂ H ₄ SO ₃ M or , B is --OM, --NH ₂ or (In the formula, R ₁ and R ₂ are H, —CH ₃ , —COOM, —N
HCOCH ₃ , —NHCONH ₂ , halogen or an alkoxy group having 1 to 3 carbon atoms, and C is (In the formula, Y is H, and (In the formula, R ₃ , R ₄ are H, -OM, -COOM, CH _{3
SO 2 -, CH 3 CONH -} , - NH 2, 1~3 carbon atoms
Represents an alkyl group, an alkoxy group having 1 to 3 carbon atoms or halogen, and m represents an integer of 0, 1 or 2) or (Wherein, p is an integer of 0, 1, 2 or 3), Z is represented _{-CH 3, -C 2 H 5,} -COOM or -NH _2, respectively); embedded image (In the formula, R ₅ is —CONH ₂ , —CH ₂ SO ₃ M, or —CN, R ₆ is an alkyl group having 1 to 4 carbon atoms, — (CH
₂ ) _q- COOM (q represents 1, 2 or 3),-(C
H ₂ ) _q —SO ₃ M (q represents the same meaning as described above) or a hydroxyalkyl group having 1 to 3 carbon atoms); (M represents the same meaning as described above) or (P represents the same meaning as described above), and n represents 0 or 1. Further, α represents a number of 1 to 3, β represents a number of 0 to 2, and γ represents a number of 1 to 4, respectively, and α + β + γ is 4 or less. Also, SO ₃ M, SO ₂ A and SO bound to Pc
Each of ₂ B is bound to a non-identical benzene ring of a phthalocyanine residue, and when Pc contains a metal, the metal is copper, zinc, aluminum or nickel, and M is H, Na or K. , Li, NH ₄ , NH ₃ CH ₂ C
H ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ or NH (C
H ₂ CH ₂ OH) ₃ . ) An ink composition comprising at least one compound represented by 2. An ink composition for producing a color filter, which comprises at least one of the compounds according to claim 1. 3. An ink composition for producing a color filter by an inkjet method, which comprises at least one of the compounds according to claim 1. 4. Using the ink composition according to claim 1,
Color filter manufactured by inkjet method.